Imparting permanent dimensional stability and finish stability to fabrics containing keratinous fibers



March 3, `1970 J. AIN

Filed March 14. 1966 FABRIC DIMENSIONAL STABILITY TO WASHING IMPARTINGPERMANENTv DIMENSIONAL STABILITY AND FINISH STABILITY TOFABRICSGONTAINING KERATINOUS FIBERS 2 Sheets-Sheet 1 PR E D Y E D l NTERNAL 8x E XTE RN AL STAB l L IZED ATTO RNEY J. cAlN 3,498,740 IMBARTINGPERMANENT DIMENSIONAI.. STABILITY AND FINISH March 3,

STABILITY T0 FABRICS CONTAINING KERATINOUS FIBERS 2 Sheets-Sheet 2 FiledMarch 14, 1966 BSVHNIHHS VBHV '|V.L0.L INVENTOR.

J. PALMER GAIN ATTORNEY United States Patent O IMPARTING PERMANENTDIMENSIONAL STABILITY AND FINISH STABILITY TO FABRICS CONTAININGKERATINOUS FIBERS James Palmer Cain, Spartanburg, S.C., assignor toDeering Milliken Research Corporation, Spartanburg, S.C., a corporationof Delaware Filed Mar. 14, 1966, Ser. No. 534,241 Int. Cl. D06m 13/14,15/52, 3/14 U.S. Cl. 8-127.6 10 Claims ABSTRACT OF THE DISCLOSURETextile fabrics containing keratinous fibers having laundry durabledimensional and finish stability are prepared by the process comprisingtreating the fabric with a polymer to externally stabilize the fabric,and treating the fabric with a reducing agent followed by leveling anddecating.

This invention relates to a textile fabric containing keratinous bersand which has substantially permanent dimensional stability and finishstability and, more specifically, to woolen fabrics having wash-and-wearcharacteristics and to the methods for producing such fabrics.

Many processes are known for the preparation of woolen or worstedfabrics having dimensional stability to machine laundering operations.None of the processes known to the prior art, however, will impart lbothdimensional stability and finish stability to a machine washable woolenfabric. For purposes of this invention, the phrase dimensional stabilityis definitive of shrink resistance, that is to say substantiallyundiminished length in both warp and fill directions, subsequent tomachine laundering. For purposes of this invention, the phrase finishstability is meant to dene lpermanent surface characteristics such as,for instance, substantially permanent luster.

-One of the few processes which have heretofore been available forimparting dimensional and finish stability incorporates an oxidativeshrink-proofing (permanganate salt) process with a reducing agent flatsetting process. This process is described in an article entitled,Washable Non-Iron Fabrics from Wool by A. J. Farnsworth, M. Lipson andl. R. McPhee in the Textile Research Journal, volume l, No. 12, Part II,December 1960, pages T1504- 1516. Particular attention is also drawn tothe first Reference cited after these articles, in the names of the sameauthors. These two processes when used in sequence on a wool fabricproduce substantial strength reductions and severely limit theapplication of the process; that is to say, the process is onlyapplicable to heavy construction fabric. If fabrics of lighter apparelweight are employed. such as fabrics now commonly used in the UnitedStates of America, strength losses are so great as to render the fabricunsuitable for garments.

Furthermore, even on the heavier fabrics, this process fails to providethe high level of finish retention which is possible by the process ofthe present invention, particularly at the low levels of shrinkage andhigh level of flat dry ratings which are produced by the presentinvention.

It is therefore an object of this invention to provide a process for thepreparation of a fabric containing keratinous fibers and havingdimensional and finish stability.

It is another object of this invention to provide a process for thepreparation of a fabric having dimensional and finish stability withoutsubstantial loss in strength.

It is a further object of this invention to provide a ICC keratinousfiber having improved dimensional and finish stability.

In accordance with this invention, it has now been discovered that aleveled keratinous fiber containing fabric having improved dimensionaland finish stability may be obtained by means of a two step processinvolving internal stabilization of the keratinous fiber and externalsta'blization of the keratinous fiber, with vthe internal stabilizationpreferably being conducted prior to the external stabilization. Thephrase internal stabilization as employed herein is deemed to includethe summation of effects achieved by treatment with a reducing agentfollowed by leveling and decating, either semi-decating orfull-decating, but preferably the latter. The internal stabilization isprimarily responsible for imparting durable finish characteristics to afabric while the external stabilization is primarily responsible forimparting durable dimensional stability to a fabric. It should beunderstood, however, that there is a unique interaction between the twostabilization treatments which results in a product having an unexpecteddegree of stability. While the external setting operation may precedethe internal setting operation, the preferred sequence is treatment witha reducing agent followed by leveling and full-decating (internalstabilization) and then conducting the external setting operation.

The term leveling as employed herein is meant to include any of thosefinishing operations commonly employed in the textile art to level andflatten the texture of a keratinous fiber containing fabric. Morespecifically, the type of leveling operation contemplated by thisinvention is a leveling operation of the type employing heat, pressureand time with or without moisture, an example of such an operation beinga sim-ple pressing operation which may be conducted with devices suchas, for instance, fixed presses, rotary presses, paper presses, orcalenders. In general, leveling pressures of from 50 p.s.i. to 50,000p.s.i. and leveling temperatures of from 70 F. to 350 F. may beemployed, preferably temperatures of from about F. to 350 F. andpressures from 1000 p.s.i. to 50,000 p.s.i. are employed. In the eventthat leveling operations are conducted by passage of the fabric into thenip of a pair of rolls, it is preferred to refer to pressures in termsof pounds per linear inch. Where a pair of pressure rolls are employedpressures in the range of from about 200 to 3,500 pounds per linear inchand preferably from 500 to 3,000 pounds per linear inch are desired.

A better understanding of the invention may be had from a description ofthe drawings wherein:

FIGURE 1 is a graph plotting percentage total area shrinkage againstwashing temperature in degrees Fahrenheit for washed prior artstabilized fabric and washed fabrics stabilized according to thisinvention.

FIGURE 2 is a graph plotting percentage total area shrinkage againstwashing temperature in degrees Fahrenheit for washed and tumble driedprior art stabilized fabric and washed and tumble dried fabricsstabilized according to this invention.

Turning to FIGURE l, all of the fabric samples ernployed in thepreparation of the graph are 100% wool twill weave fabrics having 30ends per inch and 29' picks per inch prepared from 4.0 run 11 turns perinch S twist warp and fill yarns the fabric having a loom width of 74.5inches and a finished weight of about lOl/2 ounces per yard. The sampledesignated by the solid line bearing the legend permanganate stabilizedis a fabric treated by a process which is representative of the priorart.

More specifically, this process is known as the SI-RO- NIZE process andis carried out by shrinkproofing the wool fabric with potassiumpermanganate in concentrated sodium chloride solution, the manganesedioxide being then removed with sodium bisulphite. The shrinkproofedfabric is then treated with a 1% sodium bisulphite solution so as toresult in a pickup of 50% by weight and the treated fabric steamed for 5minutes on a blowing machine.

The sample designated by the dotted line and bearing the legend postdyed internal and external stabilized is a fabric prepared according tothis invention and more specifically prepared according to Example I.The fabric designated by the broken and dotted line bearing the legendpre-dyeing internal and external stabilized is va fabric preparedaccording to this invention and more specifically prepared according toExample II. As can be seen from FIGURE 1, those fabrics which haveundergone internal stabilization prior to external stabilization exhibitstability to washing, the stability being more pronounced in the fabricthat was pre-dyed prior to stabilization as opposed to the fabric whichwas post dyed. Both the internal and external stabilized fabrics werefar superior to that fabric which is representative of the prior art.The values necessary in characterizing the stability of the fabrics wereobtained by subjecting the fabrics to washing cycles in home automaticwashing machines at varying degrees of washing temperatures and thenmeasuring the area shrinkage.

FIGURE 2 of the drawings is illustrative of the dimensional stability ofthe same fabrics set forth in FIGURE 1 with the exception that thedegree of dimensional stability is evaluated for fabrics undergoingtumble drying as well as washing cycles. It can again be noted thatthose fabrics which were subjected to internal stabilization operationsprior to an external stabilization operation exhibited superiorstability to that fabric which is representative of the prior art. Itcan also be noted that the pre-dyed internal and subsequent externalstabilized fabric exhibited a superior dimensional stability over thepost dyed sample.

The external setting of the keratinous fiber containing fabrics of theinvention is preferably accomplished by means of a polymeric chemicalreagent. Typical examples of such setting processes are additive typeshrinkproofing processes wherein polymeric reagents are added tokeratinous fabrics. These reagents preferably react with the keratinouscomponent for improved washability characteristics. It should beunderstood, however, that the external stabilization of other keratinousber may also be accomplished by means of coating the fibers with anonreactive coating composition so as to secure the fibers in thedesired configuration by means of the mechanical forces exerted by thecoating, eg. according to the WURLAN process developed at the WesternRegion Laboratories of the United States Department of Agriculture.While the preferred external setting medium is a medium of the typewhich produces new chemical bonds by reacting with a keratin fiber, theonly prerequisite for this type of reagent is that at least some of thenew chemical bonds be formed on the surface of the keratinous fiber,that is to say chemical bonds may be formed internally and externallybut at least some bonds must be formed on the surface of the fiber.Systems which have been found to be especially suitable for the externalstabilizationof this invention are interfacial polymerization systems,such as those involving the formation of poly(hexamethylene sebacate)through interfacial polymerization techniques, treatments with reactiveterpolymers based on vinyl type monomers, treatments withpolyepoxide-polyamine compositions, treatments with reactivepolyurethanes and treatments with emulsions of certain acrylic esterssuch as, for instance, polymethylmethacrylate, polyethylmethacrylate,polypropylmethacrylate and polybutylmethacrylate.

The use of polymeric external stabilizing reagents in combination withreducing agents as set forth herein has many advantages, includingbetter shrinkage controlthan is feasible with the monomeric reagents.The polymeric reagents, most importantly however, provide betterappearance retention, such as more pronounced creases or otherconfigurations, better surface qualities, such as luster, and betterflat dry ratings, than are possible with other types of reagents. Thesecompounds also may actually increase, rather than decrease, the strengthof the fabrics so treated.

This advantages are particularly evident in the use of isocyanatereaction products, which constitute highly preferred embodiment of thepresent invention.

Among the isocyanate reaction products which may be employed areisocyanate reaction products selected from two general categories, thefirst of which is a urethane prepared from a polyfunctional isocyanateand a polymeric polyhydroxy compound and the second of which is thereaction product of a polyfunctional isocyanate and polymericpolyfunctional compound selected from the group consisting ofpolyesters, polyamides, polyepoxides and reaction products of phenol andalkanol oxides, formaldehyde resins, hydrogenation products ofolefin-carbon monoxide copolymers and polyepihalohydrins. It should beunderstood that the isocyanate reaction products may be applied to thefabric as a single solution in pre-polymer form or in separate two-stepapplications following the isocyanate on the fabric in situ.

Regardless of the system utilized, however, it is preferred that theratio of isocyanate to active hydrogen compounds in the system be atleast about 0.4, but more preferably, greater than 1.0, e.g., from about1.01 to about 2.0, preferably 1.05 to 1.6.

Systems containing an excess of isocyanate are much more highly reactivewith keratin fibers, so that stabilization is provided to the desiredlevel with a minimum amount of reagent, permitting washing with littleor no egradation of hand, or feel, of the fabric. Surprisingly,configurations imparted to such fabrics by prior reducing agenttreatments are durable to washing even at low levels of polymer, e.g.,vas little as 1%, but preferablyl between 3 and 10% although amounts onthe order of 15-25% produce excellent results, even though producing astiffening effect on fabrics so treated.

By pre-polymer as employed herein is meant the reaction products of thepolyfunctional isocyanate and the preselected second polymeric compoundcarried to an extent below which a gel is produced which is insoluble inone of the organic solvents for each of the two reaction components andparticularly the chlorinated hydrocarbons.

When the prepolymer is prepared from an excess of isocyanate aspreferred, the resulting product is believed to be anisocyanate-terminated polyurethane, which is highly reactive withkeratin fibers.

Among the suitable isocyanates that may be used in accordance with thisinvention are included aryl diisocyanates such as 2,4-tolylenediisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethanediisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate,m-phenylene diisocyanate, diphenyl-4,4diisocyanate, azobenz-ene-4,4-diisocyanate, diphenylsulphone 4,4 diisocyanate, l-isopropylbenzene3, 5 diisocyanate, 1 methylphenylene 2,4 diisocyanate, naphthylene 1,4diisocyanate, diphenyl-4,4-diisothiocyanate and diisocyanate, benzene-1,2,4triisothiocyanate, 5-nitro-1,3-phenylene diisocyanate,xylylene-1,4-diisocyanate, xylylene-l,3-diisocyanate, 4,4-diphenylenernethane diisocyanate, 4,4' diphenylenepropane diisocyanateand xylylene-1,4-diisothiocyanate and the like; alicylic diisocyanates,such as dicyclohexamethane4,4diisocyanate and the like; alkylenediisocyanates such as tetramethylene diisocyanate, hexamethylenediisocyanate and the like, as well as mixtures thereof and including theequivalent isothiocyanates. Of these compounds, the aryldiisocyanatesare preferred because of their solubility and availability.

Additional isocyanates include polymethylenediisocyanates anddiisothiocyanates, and such ethylene diisocyanate, dimethylenediisocynate, dodecrnethylene diisocyanate, hexamethylene diisocyanate,tetramethylene diisocyanate, pentamethylene diisocyanate, and thecorresponding diisothiocyanates; alkylene diisocyanates anddiisothiocyanates such as propylene-l,2-diisocyanate,2,3-dimethyltetramethylene diisocyanate and diisothiocyanate,butylene-l,2-diisocyanate, b-utylene-1,3-diisothiocyanate, and butylene1,3-diisocyanate; alkylidene diisocyanates and diisothiocyanates such asethylidene diisocyanate (CH3CH(NCO)2) and heptylidenc diisothiocyanate(CH3(CH2)5CH(CNS)2); cycloalkylene diisocyantes and diisothiocyanatessuch as l,4-diisocyanatocyclohexane, cyclopentylene-1,3-diisocyanate,and cyclohexylene 1,2-diisothiocyanate; aromatic polyisocyanates andpolyisothiocyanates such as aliphatic-aromatic disocyanates anddiisothiocyanates such as phenylethylene diisocyanate diiosocyanates anddiisothiocyanates and containing heteroatoms such as SCNCH2OCH2NSC,

SCNCHZCHZOCHZCHZNSC and SCN(CH2)3S-(CH2)3NSC; 1,2,3,4tetraisocyanatobutane, butane 1,2,2-triisocyanate, toluylene-2,4,6-triisocyanate, to1uylene-2,3,4-triisocyanate, benzene-1,3,5-triisocyanate, benzene-1,2,3-triisocyanate, l-isocyanato-4-isothiocyanatohexane, and 2 chloro-1,3-diisocyanatopropane.

The preferred diisocyanates, diisothiocyanates and mixedisocyanate-isothiocyanates have the general formula ZCN-R-NCZ in which Ris a divalent hydrocarbon radical, preferably aryl, and Z is a chalcogenof atomic weight less than 33. For availability,toluylene-2,4-diisocyanate is preferred.

Any of the above isocyanate-terminated compounds, either in pre-polymeror monomer form (as in the oneshot technique) may be blocked if desired,as with phenols or any of the 'well known blocking agents forisocyanates. The blocking group is activated by heat and driven off toprovide available isocyanate groups for reaction with the functionalgroups of keratin bers.

By polymeric polyhydroxy compound is meant a linear long-chain polymerhaving terminal hydroxyl groups including branched, polyfunctionalpolymeric hydroxy compounds as set forth below. Among the suitablepolymeric polyhydroxy compounds, there are included polyether polyolssuch as polyalkyleneether glycols, andpolyalkylene-aryleneether-thioether glycols and polyalkyleneethertriols. Polyalkyleneether glycols and triols are preferred. Mixtures ofthese polyols may be used when desired.

The polyalkyleneether glycols may be represented by the formulaHO(RO)nH, wherein R is an alkylene radical which need not necessarily bethe same in each instance and n is an integer. Representative glycolsinclude polyethyleneether glycol, polypropyleneether glycol,polytrimethyleneether glycol, polytetramethyleneether glycol,polypentamethyleneether glycol, polydecamethyleneether glycol,polytetramethyleneformal glycol and poly-1,2-dimethylethyleneetherglycol. Mixtures of two or more polyalkyleneether glycols may beemployed if desired.

Representative polyalkyleneether triols are made by reacting one or morealkylene oxides with one or more low molecular weight aliphatic triols.The alkylene oxides most commonly used have molecular Weights betweenabout 44 and 250. Examples include: ethylene oxide; propylene oxide;butylene oxide; 1,2-epoxybutane; 1,2-epoxyhexane; 1,2-epoxyoctane;1,2-epoxyhexadecane; 2,3-epoxybutane; 3,4-epoxyhexane; 1,2epoxy-S-hexene; and 1,2-epoxy-3- butane, and the like. Ethylene,propylene7 and butylene oxides are preferred. In addition to mixtures ofthese oxides, minor proportions of alkylene oxides having cyclicsubstitutents may be present, such a styrene oxide, cyclohexene oxide,1,2 epoxy 2-cyclohexylpropane, and amethyl styrene oxide. The aliphatictriols most commonly used have molecular weights between about 92-and250. Examples include glycerol, 1,2,6-hexanetriol; 1,1,1-trimethylolpropane; 1,1,1-trimethylolethane; 2,4-dimethylol-Z-methylol-pentanediol-1,5 and the trimcthylether of sorbitol.

Representative examples of the polyalkyleneether triols include:polypropyleneether triol (M.W. 700) made by reacting 608 parts of1,2-propyleneoxide with 92 parts of glycerine; polypropyleneether triol(M.W. 1535) made by reacting 1401 parts of 1-2-propyleneoxide with 134parts of trimethylolpropane; polypropyleneether triol (M.W. 2500) madeby reacting 2366 parts of 1,2-propyleneoxide with 134 parts of1,2,6-hexanetriol; and polypropyleneether triol (M.W. 6000) made byreacting 5866 l parts of 1,2-pr0pyleneoxide with 134 parts of1,2,6-hexanetriol.

Additional suitable polytriols include polyoxypropylene triols,polyoxybutylene triols, Union Carbides Niax triols LG56, ILG42, LG112and the like; Jefferson Chemicals Triol G-4000 and the like; Actol32-160 from National Aniline and the like.

The polyalkylene-aryleneether glycols are similar to thepolyalkyleneether glycols except that some arylene radicals are present.Representative arylene radicals include lphenylene, naphthalene andanthracene radicals which may be substituted with various substituents,such as alkyl groups. In general, in these glycols there should be atleast one alkyleneether radical having a molecular weight of about 500for each arylene radical which is present.

The polyalkyleneether-thioether glycols and the polyalkylenearyleneetherglycols are similar to the above-described polyether glycols, exceptthat some of the etheroxygen atoms are replaced by sulfur atoms. Theseglycols may be conveniently prepared by condensing together variousglycols, such as thiodiglycol, in the presence of a catalyst, such asp-toluene-sulfonic acid.

By polymeric polyfunctional compound is meant a long-chain polymer ofthe types described containing at least two groups having at least oneactive hydrogen atom as determined by the Zerewitinot method. In theprocess of this invention, there may be utilized such compounds aspolyesters, polyamides, polyepoxides, reaction products of phenols andalkylene oxides, formaldehyde resins, hydrogenation products ofolefin-carbon monoxide copolymers, and polyepihalohydrins.

The polyesters suitable for use in accordance with this invention arewell known and are generally prepared by conducting a condensationreaction between an excess of a monomeric or polymeric polyhydroxycompound and a polyacid or by esterifying a hydroxy substituted acid anda polyhydroxy alcohol.

Among the suitable acids there are included the alkane dibasic acids,alkene dibasic acids, cycloalkene dibasic acids, cycloalkane dibasicacids, aryl dibasic acids, or any -of the foregoing types wherein thehydrocarbon radical is substituted with an alkyl, alkenyl, cycloalkyl,cycloalkenyl or aryl radical.

Representative dibasic carboxylic acids which can be employed forreaction with polyols in preparation of polyesters for use in accordancewith this invention include the following: succinic; monomethylsuccinic; glutaric' adipic; pimelic, suberic; azelaic; sebacic;brassylic; thapsic; -oxoundecanedioic; octadecanedioic acid;8-octadecenedioic acid; ricinoleic acid; 6,8-octadecadienedioic acid;malic; and the like. Other acids include unsaturated acids such asmaleic, fumarie, glutaconic, and itaconic; the cycloalkane dicarboxylicacid such as cyclopentane-l,2 dicarboxylic andcyclopentane-1,3-dicarboxylic; aromatic dicarboxylic acids such asphthalic, isophthalic, terephthalic, naphthalene-l,2-dicarboxylic,naphthalene1,3-

dicarboxylic, naphthalene-l,4-dicarboxylic, naphthalene-1,5-dicarboxylic, naphthalene-l,S-dicarboxylic, diphenyl-2,2-dicarboxylic, diphenyl-4,4'-dicarboxylic anddiphenyl2,4-dicarboxylic; and aliphatic-aromatic dicarboxylic acids suchas 2,6-dimethylbenzene-l,4-dicarboxylic acid, and4,5-dimethylbenzene-l,2-dicarboxylic acid; and the like. Naturalproducts which are particularly useful include castor oil, whichcomprises a glyceride or ricinoleic acid, and ricinoleyl alcohol, andmixtures thereof.

Represenative monomeric polyols for reaction with the above acids forthe production of polyesters for use in accordance with this inventioninclude the polyalkyleneether glycols represented by the formulaHO(RO)nH, wherein R is an alkylene radical which need not necessarily bethe same in each instance and n is an integer.

Representative glycols include polyethyleneether glycol,polypropyleneether glycol, polytrimethyleneether glycol,polytetramethyleneether glycol, polypentamethyleneether glycol,polydecamethyleneether glycol, polytetramethyleneformal glycol andpoly-1,2-dirnethylethyleneether glycol. Mixtures of two or morepolyalkyleneether glycols may be employed if desired.

Representative polyalkyleneether triols are made by reacting one or morealkylene oxides with one or more low molecular weight aliphatic triols.The alkylene oxides most commonly used have molecular weights betweenabout 44 and 250. Examples include: ethylene oxide; propylene oxide;butylene oxide; l,2epoxybutane; 1,2- epoxyhexane; 1,2-epoxyoctane;1,2-epoxyhexadecane; 2, 3-epoxybutane; 3,4-epoxyhexane;1,2-epoxy-5-hexene; and 1,2-epoxy-3-butane, and the like. Ethylene,propylene, and butylene oxides are preferred. In addition to mixtures ofthese oxides, minor proportions of alkylene oxides having cyclicsubstituents may be present, such as styrene oxide, cyclohexene oxide,1,2-epoxy-2-cyclohexylpropane, and a-methyl styrene oxide. The aliphatictriols most commonly used have molecular weights between about 92 and250. Examples include glycerol; 1,2,6-hexanetriol; 1,1,1-trimethylolpropane; l, 1,1-trimethylol`ethane;2,4-dimethylol-2-methyloldpentanediol-1,5 and the trimethylether ofsorbitol.

Representative examples of the polyalkyleneether triols include;polypropyleneether triol (M.W. 700) made by reacting 608 parts ofl,2propyleneoxide with 92 parts of glycerine; polypropyleneether triol(M.W. 1535) made by reacting l40l parts of 1,2-propyleneoxide with 134parts of trimethylolpropane; polypropyleneether triol (M.W. 2500) madeby reacting 2366 parts of 1,2-propyleneoxide with 134 parts of1,2,6-hexanetriol; and polypropyleneether triol (M.W. 6000) made byreacting 5866 parts of 1,2-propyleneoxide with 134 parts of1,2,6-h'exanetriol.

Additional suitable polytriols include polyoxypropylene triols,polyoxybutylene triols, Union Carbides Niax triols LGS 6, LG42, LGl l2and the like; Jefferson Chemicals Triol G-4000 and the like; Actol32-160 from National Aniline and the like.

The polyalkylene-aryleneether glycols are similar to thepolyalkyleneether glycols except that some arylene' radicals arepresent. Representative arylene radicals include phenylene, naphthaleneand anthracene radicals which may be substituted with varioussubstituents, such as alkyl groups. In general, in these glycols thereshould be at least one alkyleneether radical having a molecular weightof about 500 for each arylene radical. which is present.

The polyalkyleneether-thioether glycols and the polyalkylenearyleneetherglycols are similar to the above described polyether glycols, exceptthat some of the etheroxygen atoms are replaced by sulfur atoms. Theseglycols may be conveniently prepared by condensing together variousglycols, such as thiodiglycol, in the presence of av catalyst, such asp-toluene-sulfonic acid.

Additional polyesters include those obtained by reacting one or more ofthe above acids with a mixture ot polyhydric alcohols comprising (l)polyhydric alcohols of the general formula:

N-alkylene-N (alkylerieO /y wherein alkylene means a divalent saturatedaliphatic radical having at least 2 carbon atoms, preferably not morethan 5 carbon atoms, x,y and z are whole numbers and the sum of x, y andz is from 3 to l0, preferably from 3 to 6, at least two of the-(alkylene-O-}X,MH groups contain primary alcoholic hydroxyl groups andR is a large alkyl group containing from 10 to 25 carbon atoms, and (2)polyhydric alcohols containing only carbon, hydrogen and oxygen, and thepolyhydric alcohols from (l) and (2) are employed in such proportionsthat from 1 to l5 alcoholic OH groups are contributed by l) for every l0alcoholic OH groups contributed by 2).

The polyepoxides used in accordance ywith the invention are organiccompounds having at least two epoxy groups per molecule and may besaturated or unsaturated, aliphatic, cycloaliphatic, aromatic orheterocyclic. and may be substituted with non-interfering substituentssuch as hydroxyl groups, ether radicals, and the like. Polyepoxidescontaining ether groups, generally designated as polyepoxide polyethers,may be prepared as well known in the art by reacting a polyol `with ahalogen-containing epoxide employing at least 2 moles of thehalogen-containing epoxide per mole of polyol. Thus, for example,epichlorohydrin may be reacted with a polyhydric phe nol in an alkalinemedium. In another technique the halogen-containing epoxide is reactedwith a polyhydric alcohol in the presence of an acid-acting catalystsuch as hydrofluoric acid or boron triflouride and the product is thenreacted with an alkaline compound to effect a dehydrohalogenation. Apreferred example of the halogencontaining epoxide is epichlorohydrin;others are epibromohydrin, epidohydrin, 3-chloro-1,2,-epoxybutane, 3-bromo-l,2-epoxyhexane, and 3-chloro-l,2-epoxy-octane. Illustrativeexamples of polyepoxide polyethers are as follows:

1,4-bis(2,3-epoxypropoxy)benzeneg l,3-bis(2,3epoxypropoxy)benzene;4,4bis(2,3epoxypropoxy) diphenyl ether; l,8bis(2,3epoxypropoxy) octane;1,4-bis(2,3 epoxypropoxy) cyclohexane; 4,4bis(2hydroxy 2,4- epoxybutoxy)diphenyl dimethylmethane; 1,2-bis(4,5 epoxypentoxy)-5-chlorobenzene;1,4-bis(3,4 epoxybutoxy)2chlorohexane; diglycidyl thioether; diglycidylether; ethylene glycol diglycidyl ether; propylene glycol diglycidylether; diethylene glycol diglycidyl ether; resorcinol diglycidyl ether;l, 2, 3, 4-tetrakis (2-hydroxy- 3,4-epoxybutoxy butane; 2,2-bis(2,3epoxypropoxyphenyl) propane; glycerol triglycidyl ether; mannitoltetraglycidyl ether; pentaerythritol tetraglycidyl ether; sorbitoltetraglycidyl ether; glycerol di-glycidyl ether; etc. It is evident thatthe polyepoxide polyethers may or may not contain hydroxy groups,depending primarily on the proportions of halogen-containing epoxide andpolyol employed. Polyepoxide polyethers containing polyhydroxyl groupsmay also `be prepared by reacting, in known manner, a polyhydric alcoholor polyhydric phenol with a polyepoxide in an alkaline medium.Illustrative examples are the reaction product of glycerol anddi-glycidyl ether, the reaction product of sorbitol and bis(2,3epoxy2-methylpropyl)ether, the reaction product of pentaerythritol and1,2,3,5diepoxy pentane, the reaction product of2,2-bis(parahydroxyphenyl) propane and bis(2,3-epoxy2-methylpropyl)ether, the reaction product of resorcinal and diglycidylether, the reaction product of catechol and diglycidyl ether, and thereaction product of 1,4-dihydroxy-cyclohexane and diglycidyl ether.

Polyepoxides which do not contain ether groups may 9 be employed as forexample, 1,2,5,6diepoxyhexane; butadiene dioxide '(that is,1,2,3,4diepoxybutane); isoprene dioxide; lirnonene dioxide.

For use in accordance with the invention, we prefer the polyepoxides`which contain ether groups, that is polyepoxide polyethers. Moreparticularly we prefer to use the polyepoxide polyethers of the class ofglycidyl polyethers of polyhydric alcohols or glycidyl polyethers ofpolyhydric phenols. These compounds may be considered as being derivedfrom a polyhydric alcohol or polyhydric phenol by etherication with atleast two glycidyl groups The alcohol or phenol moiety may Ibecompletely etheriiied or may contain residual hydroxy groups. Typicalexamples of compounds in this category are the glycidyl polyethers ofglycerol, glycol, diethylene glycol, 2,2-bis (parahydroxyphenyl)propane,or any of the other polyols listed hereinabove as useful for reactionwith halogencontaining epoxides. Many of the specific glycidylpolyethers derived from such polyols are set forth hereinabove.Particularly preferred among the glycidyl polyethers are those derivedfrom 2,2-bis(parahydroxyphe nyl) propane and those derived fromglycerol. The cornpounds derived from the first-named of these polyolshave the structure sebacic, acid, isophthalic acid, terephthalic acid,betamethyl adipic acid, 1,2-cyclohexane dicarboxylic acid, malonic acid,polymerized fatty acids, and the like. Depending on the amine and acidconstituents and the conditions of condensation, the polyamides may havemolecular weights varying about from 1,000 to 10,000 and melting pointsabout from -200" C. Particularly preferred for the purpose of theinvention are the polyamides derived from aliphatic polyamines andpolymeric fatty acids. Such products are disclosed for example by Cowanet al. Patent No. 2,450,940. Typical of these polyamides are those madeby condensing ethylene diamine or diethylene triamine with polymericfatty acids produced from the polymerization of drying or semi-dryingoils, or the free acids, or simple aliphatic alcohol esters of suchacids.

The polymeric fatty acids may typically be derived from such oils assoybean, linseed, tung, perilla, oiticica, cottonseed, corn, tall,sunflower, safl'lower, and the like. As Well known in the art, in thepolymerization the unsaturated fatty acids combine to produce a mixtureof dibasic and higher polymeric acids. Usually the mixture contains apreponderant proportion of dimeric acids with lesser amounts of trimericand higher polymeric acids, and some residual monomeric acid.Particularly preferred are the polyamides of low melting point (about2090 C.) which may be produced by heating together an aliphaticpolyamide, such as diethylenetriamine, triethylene tetrawherein n variesbetween zero and about 10, corresponding to a molecular weight of aboutfrom 350 to 8,000. Of this class of polyepoxides it is preferred toemploy those compounds wherein n has a low value, i.e., less than 5,most preferably where n is zero.

In commerce, the polyepoxide polyethers are conventionally termed asepoxy resins even though the cornpounds are not technically resins inthe state in which they are sold and employed because they are ofrelatively low molecular Weight and thus do not have resinous propertiesas such. It is only when the compounds are cured that true resins areformed. Thus it will be found that manufacturers catalogs conventionallylist as epoxy resins such relatively low-molecular weight products asthe diglycidyl ether of 2,2 bis(parahydroxyphenyl) propane, thediglycidyl ether of glycerol, and similar polyepoxide polyethers havingmolecular weights substantially less than 1,000.

It is Within the purview of the invention to employ mixtures ofdifferent polyepoxides. Indeed, it has been found that especiallydesirable results are attained by employing mixtures of twocommercially-available polyepoxides, one being essentially a diglycidylether of glycerol, the other being essentially a diglycidyl ether of2,2- bis(parahydroxyphenyl) propane. Particularly preferred to attainsuch result are mixtures containing more than 1 and less than 10 partsby weight of the glycerol diglycidyl ether per part by weight of thediglycidyl ether of 2,2-bis (parahydroxyphenyl) propane.

The polyamides used in accordance with the invention are those derivedfrom polyamines and polybasic acids. Methods of preparing thesepolyamides by condensation of polyamines and polycarboxylic acids arewell known in the art. One may prepare polyamides containing free aminogroups or free carboxylic acid groups or both free amino and freecarboxylic acid groups. The polyamidesy may be derived from suchpolyamines as ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, 1,4 diaminobutane, 1,3diaminobutane, hexamethylene diamine, 3-(N-isopropylamino) propylamine,3,3 iminio bispropylamine, and the like. Typical polycarboxylic acidswhich may be condensed with the polyamines to form polyamides areglutaric acid, adpic acid, pimelic acid, suberic acid, azelaic acid,

mine, 1,4-diaminobutane, 1,3-diaminobutane, and the like with thepolymerized fatty acids. Typical among these is a polyamide derived fromdiethylene triamine and dimerized soybean fatty acids. The polyamidesderived from aliphatic polyamides and polymerized fatty acids, like thepolyepoxides, are often referred to in the trade as resins even thoughnot actually resins in the state in which they are sold and applied.Particularly good results are obtained in the use of low molecularWeight, non-fiber forming polyamides sold under the trade name ofVerSamids.

Any suitable condensation product of a phenol and an alkylene oxide maybe used such as, for example, the condensation product of cresol or4,4-isopropylidenedi phenol with one of the aforementioned alkyleneoxides.

Any suitable hydrogenation product of olens-carbon monoxide copolymersmay be used such as, for example, the hydrogenation product of anethylene-propylene-carbon monoxide copolymer and others disclosed inU.S. Patent 2,839,478, issued to Wilms et al. June 17, 1958, and U.S.Patent 2,495,292, issued to Scott, Ian. 24, 1950.

In the -process of this invention, it is preferred to react thepolyfunctional isocyanates and polymeric polyfuntional compound orpolyfunctional isocyanate and polymeric polyhydroxy compound as the casemay be with or without a coreactant and unblocked or blocked with thekeratinous bers in the presence of a catalyst. Any of the well-knowncatalyst for the reaction of active hydrogen atoms with isocyanates maybe used. Of these catalysts which are used in the production ofpolyurethanes the organo-tin compounds are preferred, particularlystannous octoate.

The various isocyanate reaction product systems described abovepreferably are applied to the keratinous fiber containing fabric in theform of a solution, the solution employing a non-reactive solventalthough aqueous emulsions may be utilized if desired. By non-reactiveas used herein is meant a solvent in which reactivity between theisocyanate and active-hydrogen containing components even in thepresence of catalyst is substantially inhibited. Small amounts ofreactive solvents may be present provided the amount present issufficiently low as not to precipitate a substantial amount of thecomponents with which it is reacted. In other words, sufficientcomponents remain reactive with the keratin fibers to provide adequateinhibition of shrinkage and/or setability in the fabric or otherstructure being treated.

Suitable organic solvents include halogenated hydrocarbons such astrichloroethylene, methylene chloride, perchloroethylene, ethylenedichloride, chloroform and the like; aromatic solvents such as toluene,oxylene, benzene, mixed aromatics, such as the Solvesso types and thelike, n-butyl acetate, n-butyl ether, n-butyl phosphate, p-dioxane,ethyl oxalate, methyl isobutyl ketone, pyridine, quinoline,N,Ndimethylforrnamide, N,Ndimethy1- acetamide, dimethyl sulfoxide, 2,2,4trimethyl pentane and the like. Mixtures of solvents may be used.

The internal setting of the keratinous fibers is preferably accomplishedby means of a chemical reagent which has the ability to rupturepolymeric linkages, particularly disulfide linkages, within thestructure of keratin. These ruptured linkages may be at least partiallyreformed while holding the keratinous fiber in the desiredconfiguration, thereby setting this configuration durably in the fiber.The preferred chemical reagent for accomplishing the aforementionedsplitting and reformation of polymeric linkages is a reducing agent. Thereaction which appears to take place in setting the keratinous fibers inthe new shape is reformation of the cystine linkage and reformation ofhydrogen -bonds and hydrophobic bonds of the keratinous fibers, thebonds and linkages having previously been split by contact with thereducing agent. The cystine linkages are split and reunited to form atleast some of the disulfide bonds. While the keratinous fibers remainsubstantially unchanged chemically by the reduction and oxidationoperations, some relocation of the cystine linkages apparently takesplace along with Some changes in hydrogen and/or hydrophobic bonding.These changes in location of cystine linkages and changes in hydrogenand/or hydrophobic rbonding produce a reformed fi-ber. The reformationof the fiber gives the individual keratinous fibers of this inventiontheir internal setting which results in a fabric which has stabilizationto finish changes.

It should be understood that the objective of rupturing thecharacteristic linkages of keratin followed by a reformation of thelinkages when the fiber is in the desired geometric configuration may beaccomplished to some extent `by the use of steam. Where, however,maximum setting of the keratinous fibers is desired, a reducing agentshould be employed. Among the suitable reducing agents, there areincluded lower alkanolamine sulfites such as monoethanolamine sulfiteand isopropanolamine sulfites, and others containing up to about 8carbon atoms in the alkyl chain, such as n-propanolamine sulfite,n-butanolamine sulfite, dimethylbutanolamine sulfite, dimethylhexanolamine sulfite and the like; metallic formaldehyde sulfoxylates,such as zinc formaldehyde sulfoxylate; the alkali metal lsulfoxylates,such as sodium formaldehyde sulfoxylate and potassium formaldehydesulfoxylate; the alkali metal borohydrides, such as sodium borohydride,potassium borohydride and sodium potassium borohydride; alkali metalsulfites, such as sodium or potassium bisulfite, sulfite, metabisulfite;ammonium bisulfite, sodium sulfide, sodium vhydrosulfide; sodiumhypophosphite; sodium thiosulfate, sodium dithionate, titanous chloride;sulfurous acid; mercaptan acids, such as thioglycollic acid and itswater soluble salts, such as sodium, potassium or arnmoniumthioglycolate; mercaptans, such as hydrogen sulfide, alkyl mercaptanssuch as butyl or ethyl mercaptans and mercaptan glycols, such as-mercapto ethanol; and mixtures of these reducing agents.

Particularly beneficial results are obtained if the reducing agent isemployed in conjunction with a 10W molecular Weight polyhydroxy compoundor other auxiliary agent. Urea constitutes the most readily availableand desirable auxiliary agent, although any other material which willswell keratinous fibers in an aqueous medium is suitable. For example,guanidine compounds such as the hydrochloride; formamide, N,Ndimethylformamide, acetamide, N,N dimethylacetamide, dimethyl sulfoxide,thiourea, phenol, lithium salts, such as the chloride, bromide, andiodide and the like are similarly useful.

By the term low molecular weight polyhydroxy compound is meant acompound containing more than one hydroxy group and having a molecularweight preferably no greater than about 4000. Of these compounds, themost readily available and desirable compound, from the standpoint ofease of application, comprises ethylene glycol. A particularly preferredgroup of glycols includes the polyfunctional glycols having terminalhydroxy groups separated by 2 to 10 methylene groups, including ofcourse, the preferred ethylene glycol as well as trimethylene glycol,tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, anddecamethylene glycol, or such glycols as 1,2-propylene glycol,dipropylene glycol, 1,3- 1butylene glycol, diethylene glycol,polyethylene glycol 0r the like.

Polyfunctional compounds containing more than 2 hydroxyl groups includethe polyfunctional alcohol glycerols such as glycerine anddiethylglycerol as well as trimethylol ethane, trimethylol butane,tris-hydroxymethyl-amino methane and others. Glycol ethers, such as thewater-soluble or dispersible polyethylene glycols or polypropyleneglycols having molecular weights preferably no greater than about 4000also provide satisfactory results when utilized in accordance with thisinvention.

The reducing agent with or without the auxiliary agent or polyhydroxycompound may be applied to the fabric in any desired amount, dependingupon the degree of reducing desired. In general, optimum results areobtained when aqueous solutions containing from about 0.01 t0 about 20%by weight and most preferably from 1 to about 10% by weight of thereducing agent is applied to the fabric. The swelling agent orpolyhydroxy compound if employed may be applied to the fabric byaddition to the aqueous solution of reducing agent of amounts of fromabout 3 to about 30% and most preferably from about 5 to about 20% byweight. Higher concentrations may be utilized where the fabric is to beexposed to the treating medium for only a short time.

The reducing agent may be applied to the fabric by methods such as, forinstance, spraying padding, squeezing, simple immersion, and wettingwith blankets saturated with reducing solutions. It is desirable thatthe reducing agent treated fabric be given time for the reducing agentto distribute and react before lthe fabric is subjected to lusteringoperations. After the reducing agent treated fabric has been aged, it ispreferably dried, the drying operation being sufficient to reduce themoisture content of the fabric to the point that substantial setting ofthe fabric is not accomplished prior to the decating operations. In someinstances, however, a special finish may be imparted by allowingsufficient moisture to remain in the fabric to accomplish partialsetting of the fabric in a leveling operation, the complete permanentsetting preferably being accomplished by a full-decating operation. Thepreferred leveling operation is a calendering operation.

The calendering operation is preferably carried out at elevatedtemperatures, that is from about F. to about 350 F. and most preferablyfrom about 250 F. to 300 F. Calendering pressures are in the range offrom about 1/2 ton per linear inch to about 2 tons per linear inch andpreferably from about l ton per linear inch to about 11/2 tons perlinear inch. The upper limit for calendering pressures may be higher,the only real limitation imposed is the maximum pressure which may beobtained from calendering apparatus. It should be understood that thecalendering operation is always carried out under conditions which willproduce chiefly a temporary setting with little or no permanent settingof the keratinous bers of the fabric. The calendered fabric is then sentinto the preferred full-decating operation, the full-decating operationemploying a steam interval of from about 1 minute utes to about 6minutes and a vacuum interval of from about 2 minutes to about 60minutes and preferably from about 10 minutes to about 30 minutes. Thesteaming operation is carried out at autoclave pressures of from about 1p.s.i. to about 100 p.s.i. gauge and preferably from about p.s.i. gaugeto about 40 p.s.i. gauge. The steam pressures, of course, will alsodetermine the temperatures employed.

It is preferred that the stabilized fabric of this invention besubjected to an aldehyde treatment in order to enhance still further thedurability of the finished product. The aldehyde may be present in thereducing agent both in the form of an organic compound which releasesaldehyde on thermal decomposition at temperatures such as areencountered in full-decating operations or may be applied as a separateoperation subsequent to the reducing agent treatment. The fabric must,however, be in its preferred configuration prior to being subjected tothe action of an aldehyde. Compounds which will release an aldehyde onthermal degradation are also suitable for separate application after thereducing agent treatment provided that the thus treated fabric must gothruogh a nal heating operation such as in a curing oven. Suitablecompounds which release aldehydes on thermal degradation and which maybe incorporated in the reducing agent solution for simultaneousapplication are compounds having the general formula:

wherein R is a member selected from the group consisting of (1) -CH3 (2)-fC2H5 (4) -n-butyl (5) -iso-butyl. When compounds of this type areincorporated in the reducing agent bath, the reducing must be of thetype which will not undergo an organic reaction with the thermallydegraded compound. For this reason, it is preferred that inorganicreducing agents Ibe employed in conjunction with the thermallydegradable compound.

Typical aldehydes which may be applied subsequent to application of areducing agent include formaldehyde, saturated aliphatic aldehydes, suchas acetaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde,valeraldehyde, isovaleraldehyde, caproaldehyde, enanthaldehyde,caprylaldehyde, pelargonaldehyde, capraldehyde, lauraldehyde, palmiticaldehyde, stearaldehyde and the like; unsaturated aliphatic aldehydes,such as acrolein, crotonaldehyde, tiglic aldehyde, citronellal, citral,propiolaldehyde, and the like; alicyclic monofunctional aldehydes, suchas formylcyclohexane and the like; aliphatic dialdehydes, such asglyoxal, pyruvaldehyde, malonaldehyde, succinaldehyde, glutaraldehyde,adipaldehyde, maldealdehyde and the like; substituted aldehydes, such aschloral, aldol and the like; aromatic aldehydes wherein the aldehydegroup is attached to a ring, such as benzaldehyde, phenylacetaldehyde,p-tolualdehyde, p-isopropylbenzaldehyde, o-chlorobenzaldehyde,o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde,salicylaldehyde, anisaldehyde, vanillin, veratraldehyde, piperonal,a-naphthaldehyde, antraldehyde and the like; and aromatic aldehydeswherein the aldehyde group is not attached to a ring, such asphenylacetaldehyde, cinnamaldehyde and the like; and heterocyclicaldehydes, such as a-formylthiophene, a-formylfurfural, furfural,tetrahydrofurfural and the like.

Typical aldehyde generating compounds suitable for applicationsubsequent to but not simultaneously with application of the reducingagent include linear polymers, particularly those of the general formulawhich depolymerize to monomeric formaldehyde gas upon vaporization. Inthis class of compounds, there are included lower polyoxymethyleneglycols, wherein n is from about 2 to about 8; paraformaldehyde, whereinn ranges from about 6 to about 100; alphapolyoxymethylenes, wherein n isgreater than about 100; beta-polyoxymethylene wherein n is greater thanabout 100 and a trace of H280.,A is present, and the like.

'Polyoxymethylene glycol derivatives may also be utilized, e.g., such asthe polyoxymethylene diacetates, the lower polyoxymethylene dimethylethers, gamma-polyoxymethylenes (higher polyoxymethylene dimethylethers), delta-polyoxymethylenes, epsilon-polyoxymethylenes and thelike. In general, higher temperatures, e.g., up to about 200 C. areutilized to effect depolymerization of these derivatives. In manyinstances, depolymerization, with formaldehyde generation, is mostreadily effected by treatment with dilute alkali or acid to produce thecorresponding glycol which can then tbe hydrolyzed to formaldehydesolutions.

Formaldehyde acetate (formals) may also be utilized. Preferred formalsare produced by reaction of formaldehyde with alcohols of the formulalCH2(OR)2 in the presence of an acid catalyst, wherein R is alkyl ofaralkyl. These compounds hydrolyze to formaldehyde and the parentalcohol. Preferred formals include methylol and 1,3-dioxolane. Thelatter compound hydrolyzed to formaldehyde and ethylene glycol and isparticularly preferred among this class of compounds when used inpresensitizing processes.

Additional suitable generating compounds include the Various methylolcompounds, for example, methylolalkanolamine sultes, such as4N-methylolethanolamine sulite, N,Ndimethylolethanolamine sulite,N,Ndimethyl olisopropanolamine suliite and the like; methylol amides,such as N-methylolformamide, N-methylolacetamide, N- rnethylolacrylamideand the like; amines, such as hexamethylene tetramine,trimethylolmelamine and the like; and compounds such as the alkali-metalformaldehyde bisultes, including sodium and potassium formaldehydebisulftes.

The process of this invention is applicable to any keratinous substrate,including, of course, fabrics made from blends of keratinous fibers withother natural fibers, including silk, cellulosic iiber and the like, orwith synthetic bers, such as synthetic cellulosic 'bers includingacetylated cellulose, for example, the cellulose acetates, acetylatedrayon, rayon per se and the like; polyamides, particularly nylon, both 6and 66 types; polyesters, such as polyethylene terephthalate and thelike; polyolens, such as polyethylene, polypropylene and the like;acrylic fibers, such as those produced from acrylonitrile and copolymersthereof, and the like.

It is preferred, however, that a substantial amount of keratinousfibers, for example at least about 20%, preferably at least about 40%,by weight be present in the substrates being treated.

The following examples of the preparation of the internally andexternally stabilized fabric of this invention are given for purposes ofillustration and should not be considered as limiting the spirit orscope of this invention.

EXAMPLE I An all Wool twill weave fabric (10.5 oz./linear yard- 60inches wide) which has been preconditioned to remove excess residualoils, sizes and vegetable matter and which has been prepared bymechanical wet finish techniques to impart desired bulking or otherproperties is padded with a solution of 2.6% sodium bisulfte, 2.85%diammonium phosphate and 0.25% Syn-O-Wet HR (anionic surface activeagent marketed by Syn-Chem Corporation) to 70% wet pickup and dried at225 F. to approximately 10% moisture regain. The fabric is thencalendered in a conventional roll calender at tons pressure across 72inch roll-face and at a roll temperature of 280 F. This flattened fabricis then placed in a full decater package and autoclaved at 12 p.s.i.gauge steam using a cycle of 51/2 minutes penetration followed by 21/2minutes outside to inside steam iiow and 21/2 minutes inside to outsidesteam iiow. The entire autoclave package is then subjected to vacuumpumping for 20 minutes.

A polymeric coating composition is then prepared as follows: Into ajacketed stainless steel reactor is poured 225 pounds of polypropyleneglycol adduct of glycerin having a molecular weight of about 5000. Thereactor is then closed and the pressure therein reduced to about rnm.mercury after which the reactor is flushed with dry nitrogen. Thepressure regulation and flushing operation is repeated for 3 cycles,after which 23 pounds of dry toluene is poured into the reactor. Ablanket of nitrogen gas is maintained in the vessel throughout thereaction. The pressure is again reduced to 10 mm. mercury and thereactor is heated to 140 C. to distill off the toluene, after which itis cooled to room temperature using cold water in the jacket around thereactor. The pressure is returned to room conditions. After stirring forminutes to thoroughly mix the components about twice the stoichiometricquantities for reaction with the glycol of tolylene-2,4-diisocyanate isadded rapidly and stirred until the heat of reaction ceases and thetemperature has risen slowly up to 40-45 C. from room temperature ofabout 28 C. The reaction mix is then heated at a rate of about 2 C. perminute to a temperature of 146 C. where it is held for 18 minutes andthen cooled at a rate of about 2 C. per minute to a maximum temperatureof 100 F. Sufficient trichloroethylene is then added to provide asolution containing 70% of the resulting pre-polymer. The pre-polymersolution is then transferred from the reactor to a pre-dried drum undera dry nitrogen atmosphere to avoid water contamination. At the time ofthe transfer, the pre-polymer solution has a color of from colorless toa very pale straw color.

A 3% solution is then prepared from a 70% solution of pre-polymer bydilution with trichloroethylene and the fabric padded to a wet pickup of100%, the pad bath containing Quadrol (N,N,N,Ntetrakis 2-hydroxy propylethylene diamine marketed by Wyandotte Chemical Corporation), the fabricbeing dried lat about 160 F. and cured at about 260 F. The fabric thustreated is allowed to `set for 16 hours. scoured in a cascade washer andthen placed in a dyebeck for dyeing. After dyeing with normal wash-fastwool dyeing techniques, the fabric is then dried, padded with a 5.5%solution of formalin (2.0% formaldehyde) to approximately 70% wet pickupand dried at 225 F. to a moisture regain of 10%. After drying the fabricis full decated at 12 p.s.i. for 3 minutes, pumped for 10 minutes andinspected. The resulting fabric has excellent dimensional stability andlfinish stability to home laundering at 140 F. in a Kenmore Model 600washing machine less than 1 year old, set at the Normal cycle andcontaining 10 grams of Tide detergent.

EXAMPLE II The procedure of Example I was again repeated with theexception that the fabric was dyed prior to application of the solutionof 2.6% sodium bisulte. The finished product is found to have excellentdimensional stability and Ifinish stability to home laundering at 140 F.in a Kenmore Model 600 washing machine less than 1 year old, set at theNormal cycle and containing 10 grams of Tide detergent.

EXAMPLE III The procedure of Example I is again repeated with theexception that the application of the 5.5 solution formalin is omitted.The resulting fabric is found to have good dimensional stability andfinish stability to home laundering at 140 l5", in a Kenmore Model 600washing machine less than 1 year oid, set at the Normal cycle andcontaining 10y grams of Tide detergent.

EXAMPLE IV The procedure of Example II is again repeated with theexception that the application of the 5.5% solution of formalin isomitted. The resulting fabric is found to have good dimensionalstability and finish stability to home laundering operations at 140 F.in a Kenmore Model 600 washing machine less than l year old, set at theNormal cycle and containing 10 grams of Tide detergent.

EXAMPLEV A 55% Acrilan (acrylic fiber marketed by Chemstrand Division ofMonsanto Co.)/45% woolen flannel fabric which has been preconditioned toremove excess residual oils, sizes and vegetable matter and which hasbeen prepared by mechanical wet finish techniques to impart desired bulkand then placed in a dyeing beck for dyeing with normal wash-fast wooldyeing steps. The fabric is then padded, dried and cured With theurethane polymer according to procedure set forth in Example I. Thefabric is allowed to stand for 11 hours and then scoured in a cascadewasher. The fabric is then padded with a solution of 6.4%monoisopropanolamine sulte, 2.85% diammonium phosphate and 01.25%Syn-O-Wet HR to 70% wet pickup and dried at 225 F. to approximately 10%moisture regain. The fabric is then calendered in a conventional rollcalender at tons pressure across 72 inches roll face and at a rolltemperature of 280 F. The flattened fabric is then pressed in a fulldecater package autoclaved at 12 p.s.i. gauge steam using a cycle of 5minutes penetration followed by 2 minutes outside to inside steam ow and2 minutes inside to outside steam. The entire autoclave package is thensubjected to vacuum pumping for 20 minutes. The yfinal product is foundto have good dimensional and yfinish stability to home laundering at F.in a Kenmore Model 600 washing machine less than 1 year old, set at theNormal cycle and containing 10 grams of Tide detergent.

EXAMPLE VI The procedure of Example V was again repeated with theexception that the fabric was dyed as a final operation subsequent tothe full-decating operation. The yfinal product is found to have gooddimensional and finish stability to home laundering at 140 F. in aKenmoreModel 600 washing machine less than 1 year old, lset at theNormal cycle and containing 10 grams of Tide detergent.

EXAMPLE VII The procedure of Example V was again repeated with theexception that prior to full-decating the fabric is dried, padded to 5.5wet pickup with formalin (2.0% formaldehyde) and dried at 225 F. to amoisture regain of 10%. The final product is found to have excellentdimensional and finish stability to home laundering at 140 F. in aKenmore Model 600 washing machine less than l year old, set at theNormal cycle and containing 10 grams of Tide detergent.

EXAMPLE VIII A 55 polyester/45% wool worsted fabric is padded with 2.6%sodium bisulte, 2.8% diammonium phosphate and 0.25% Syn-O-Wet HR. Thisfabric is dried at l225 F. to 8% moisture regain, calendered at 50 tonspressure across 72 inch face rolls, placed in a full decater package andautoclaved for 5 minutes. The package is subsequently pumped for 15minutes. The fabric is then treated with the urethane polymer as inExample I, scoured and dyed with normal wash-fast polyester and wooldyeing techniques and dyestuffs. After dyeing and drying the fabric ispadded with a solution of 5% available formaldehyde in the form of a 25%solution of N-methylol methylcar'bamate, dried at 200 F. to 8% moistureregain, placed in a full decater package and autoclaved for minutesafter penetration. The fabric shows excellent dimensional and finishstability to Washing in a Kenmore Model 600 washing machine less than 1year old, set at the Normal cycle and containing grams of Tide detergentand tumble drying at 180 F. in a Kenmore Model 600 dryer.

EXAMPLE IX The procedure of Example VIII is again repeated with theexception that in place of treatment with the urethane polymer, thefabric is immersed in a 3.3% aqueous solution of polyaminocaproic aciddiethyl amino ethynol derivative, the specic means of preparation ofwhich is set forth in U.S. Patent No. 2,696,448. Excess pad liquor isremoved bypassing the fabric through squeeze rollers. The fabric isdried at about 80 C., cured at 130 C. for minutes, scoured and dyed.After undergoing the remaining portion of the treatment, the fabric isfound to have excellent dimensional and finish stability to washing in aKenmore Model 600 washing machine less than 1 year old, set at theNormal cycle and containing l0 grams of Tide detergent and tumble dryingat 180 F. in a Kenmore Model 600 dryer.

EXAMPLE X The procedure of Example VIII is again repeated with theexception that in place of treatment with the urethane polymer, thefabric is dipped into an emulsion prepared as follows: (a) 4 grams ofthe polyester reaction product of adipic acid and glycerol is dissolvedin 4 milliliters 0f methylethyl ketone (b) 4 grams of 2,2 bis(2,3-epoxypropoxy phenyl) propane was dissolved in 4 milliliters ofmethylethyl ketone (c) 4 grams of polyamide condensation product ofdiethylene triamine and dimerized unsaturated fatty acid was dissolvedin 4 milliliters of methylether ketone. The 3 solutions of (a), (b), and(c) are then mixed together and the composite solution poured into 375milliliters of water with stirring so as to form an emulsion. The fabricis then dipped into the emulsion and passed through squeeze rolls so asto give a weight increase of 65%. The impregnated fabric is air dried toabout 30% moisture and then heated in an oven for 30 minutes at 250 F.,scoured and dyed. After undergoing the remaining portion of thetreatment, the fabric is found to have excellent dimensional and nishstability to washing in a Kenmore Model 600 washing machine less than 1year old, set at the Normal cycle and containing 10 grams of Tidedetergent, and tumble dryingat 180 in a Kenmore Model 600 dryer.

and decating are utilized. This fabric is designated Fabric A in Table Ibelow.

The procedures utilized in producing Fabric A are repeated on anadditional sample of fabric, except that the formalin post-treatmenttechnique of Example I, including decating, is utilized. The fabric soproduced is designated Fabric B in Table I below.

An additional sample of the all wool twill weave fabric is treated witha sodium bisuliite solution and calendered and steamed as set forth inExample I. No pre-polymer or formalin treatments are conducted. Thisfabric is designated Fabric C in Table I below.

The procedures utilized to produce Fabric C are repeated on anadditional fabric sample except that the formalin post-treatment,including decating, is utilized. This fabric is designated Fabric D inTable I.

On additional samples of the all wool fabric, the procedures of ExampleI are reproduced, with and without the formalin post-treatment. Thesefabrics are designated Fabrics E and F, respectively, in Table I.

The procedures of Example I are repeated on additional samples of fabricexcept that the reactive polymer treatment is conducted prior to thelevelling and reducing agent treatments, and with and without theformalin posttreatment. These fabrics are designated Fabrics G and H inTable I.

The procedures of Example I are repeated on another sample of the allwool fabric, except that a 3% solution of Zeset TP (believed to -be theterpolymer of ethylene, vinyl acetate and methacroyl chloride) issubstituted for the pre-polymer solution, and except that the formalinpost-treatment is not conducted. This fabric is designated Fabric I inTable I.

Samples of each of the above fabrics are washed ten (l0) times under theconditions of Example I, after which the Flat Dry rating for spinperformance is measured by the standard appearance test using overheadlighting on vertically hanging fabrics. The fabrics are rated from 1.0(poorest) to 6.0 (best). The shrinkage of these samples in both warp andfilling directions also is measured.

Additional samples of each fabric are subjected to ten (l0) washing anddrying cycles, the washing being performed as in Example I and drying asin -Exarnple VIII. The Tumble and Flat Dry rating and shrinkage aremeasured after these cycles. Furthermore, the fabrics are rated byobjective observers to determine the degrees to which the initiallustrous appearance of the fabric is retained.

All the above measurements are set forth in Table I.

TABLE I Washing and tumble Flat dry Washing shrinkage drying shrinkageLuster retained Fabric Spin Tumble Warp Fill Warp Fill percent Fabn'cA-Reactive pre-polymer, no reducing agent, no HCHO 4. 0 5. 0 3. 0 2. 34. 2 3, 1 None Fabric B-Reactive pre-polymer, no reducing agent, WithHCHO 4.2 5.0 3. 8 2. 1 4. 2 3. 1 Non@ FabriIcICCH-educing agent, noprepolymer, 4 9 3 Fabiii i135 Rduc 4 9 5 o 25 o None wi 36. 1 27. 0 39.5 25. 5 on Fabric E-Reducing agent, reactive pre- N e polymer, HCHO 4. 55. 0 1. 8 1. 0 2. 0 1. 8 90 Fabric F-Redueing agent, reactivepre-polymer, no HCH() 4. 5 5. 0 1. 0 0. 6 3. 0 4. 8 60 Fabric G-Reactivepre-polymer, reducing agent, HC O 4. 4 5. 0 4. 5 0.8 5. 2 1. 2 90 FabricIii-Reactive pre-polymer, reducing agent, no HCHO 4. 5 5. 0 1. 0 0. 7 3.9 4. 1 70 Fabric I-Reducing agent, Zeset TP, no

HCHO 4.8 5.0 3:8 -1.3 5.2 0.6 90

The minus values of shrinkage of Fabric I indicates that the fabricstretched to the levels shown.

IEXAMPLE XI EXAMPLE XII An all 4will twill weave fabric is impregnatedwith an aqueous solution containing 1% hexamethylene diamine, 2% sodiummetasilicate and 0.05% Triton X100 (isooctylphenol reacted with 9 to 10ethoxy groups) to a wet pickup level of 70%. The wet fabric is thenimmersed in steaming a 3% solution of sebacoyl chl-oride in Solvesso 100(a 19 mixture of aromatic hydrocarbons) to an additional wet pickup of20%. y

After scouring for 15 minutes at 120 F. with a 1% solution of formicacid containing 0.1% Triton X-100, the fabric is rinsed in clear Waterfor minutes at 120 F. and dried.

The externally stabilized fabric is then padded to 20% Wet pickup withan aqueous solution containing 2% sodium bisulfite and 0.1% Syn-O-WetHR. After drying at 200 F., the fabric is full-decated according to theconditions of Example I, then washed, tumble dried and tested as inExample XI. After washing ten times, the shrinkage values in the Warpand filling directions are 2.6 and 5.2, respectively. Correspondingvalues after washing and tumble drying ten (l0) times are 5.6 and 7.4,respectively. The Spin and Tumble Flat Dry ratings are, respectively,4.3 and 4.9. Visual observation indicated about 60% of the lustrousfinish was retained.

Having thus disclosed the invention, what is claimed is:

1. A process for imparting laundry durable dimensional and nishstability to fabrics containing at least some keratinous fibers, saidprocess comprising (a) treating the fabric with a polymer and curing thepolymer on the fabric to externally stabilize the fabric,

(b) treating the fabric with a reducing agent capable of rupturing thevcystine linkages of the keratin fiber,

(c) leveling the reducing agent treated fabric at a temperature andpressure insufficient to permanently set the bers, and

(d) decating the leveled fabric.

2. The process of claim 1 Iwherein the reducing agent treatment precedesthe polymer treatment.

3. The process of claim 1 wherein the polymer is a urethane polymer.

4. The process of claim 3 wherein the urethane polymer contains freeisocyanate groups.

5. The process of claim 1 wherein the polymer s a reactive polyethylene.

6. The process of claim 1 wherein the leveling is produced by acalendering operation.

7. The process of claim 6 wherein the calendering is conducted at atemperature between about and 350 F. at a surface pressure of from about0.5 ton to 1.5 tons per linear inch.

8. The process of claim 1 wherein the decated fabric is subsequentlytreated with an aldehyde.

9. The process of claim 8 wherein the aldehyde is formaldehyde.

10. A fabric obtained by the process of claim 1.

References Cited UNITED STATES PATENTS 2,508,713 5/1950 Harris et al.8-127.6 2,524,042 10/1950 Croston et al. 8-127.6 2,678,287 5/1954 Cuperyet al. 8-127.6 X 2,689,194 9/1954 Russell et al. 8-l15.6 X 2,933,4094/1960 Binkley et al 8127.6 X 3,084,018 4/1963 Whitfield et al. 8 1283,098,694 7/1963 Reider 8-128 3,112,984 12/1963 Aldridge 8127.6 X3,151,439 10/1964 Dusenbury 8-128 X RICHARD D. LOVERING, PrimaryExaminer U.S. Cl. X.R.

